Porous water-soluble nonionic cellulose ether having excellent solubility and method for producing the same

ABSTRACT

There are provided a porous water-soluble nonionic cellulose ether having an average pore size of 36 μm or smaller and an average particle size of from 30 to 300 μm; and a method for continuously producing said cellulose ether comprising the steps of: pulverizing a first water-soluble nonionic cellulose ether to obtain a first pulverized product, and sieving the pulverized product through a sieve having an opening of from 40 to 400 μm to obtain a first residue-on-sieve and a first sieve-passing fraction, wherein a portion or all of the first residue-on-sieve containing particles having particle sizes smaller than and greater than the opening of the sieve is re-pulverized together with a second water-soluble nonionic cellulose ether in the step of pulverizing to obtain a second pulverized product, which is pulverized to obtain the cellulose ether as a second sieve-passing fraction containing the re-pulverized particles.

RELATED APPLICATION

The present application is a divisional of U.S. application Ser. No.15/333,616, filed Oct. 25, 2016, which claims priority to JapanesePatent Application No. 2015-211073, filed Oct. 27, 2015, the disclosuresof which are incorporated by reference in their entireties.

BACKGROUND OF THE INVENTION 1. Field of the Invention

The present invention relates to a porous water-soluble nonioniccellulose ether having excellent solubility and being used in chemicalfields, pharmaceutical fields and the like; and a method for producingthe porous water-soluble nonionic cellulose ether.

2. Description of the Related Art

A water-soluble nonionic cellulose ether has been used as apharmaceutical product, a food binder, a disintegrant, a thickeningagent of various solvents, a water retention agent for buildingmaterials, a binder for extrusion, a suspension stabilizer, and thelike.

A water-soluble nonionic cellulose ether is often required to be kneadedwith a small amount of water to dissolve therein. When it is kneadedwith a small amount of water and dissolved therein, a surface portion ofwater-soluble nonionic cellulose ether powder or grains dissolved firstin water sometimes forms a highly tacky film during dissolution. Thishighly tacky film allows the water-soluble polymer powder or grains toadhere to each other by stirring during dissolution to form largeparticles in lump form. In this case, it takes long hours to dissolvethem in water because of uneven distribution of water. For this reason,dissolution of water-soluble polymer such as methyl cellulose,hydroxypropyl methyl cellulose and hydroxyethyl methyl cellulose iscarried out by a complicated method such as a method comprising thesteps of: dispersing such a cellulose ether in hot water in advance bytaking advantage of the property that the cellulose ether is insolublein hot water of 90° C. or more, and then cooling the resultingdispersion gradually. On the other hand, dissolution of water-solublepolymer such as polyethylene oxide and sodium polyacrylate is carriedout by a complicated method such as a method comprising the steps of:dispersing the polymer in water in a particularly high-speed stirringapparatus, while preventing formation of lumps, and then converting theresulting dispersion to a solution by stirring.

As a method for producing a water-soluble nonionic cellulose ether whichcan be dissolved without formation of lumps in cold water, there isproposed a method comprising the steps of: adding 0.01 to 15 parts byweight of at least one plasticizer selected from ether-, ester-, andamine-based plasticizers to the water-soluble nonionic cellulose etherpowder, and after uniform mixing and drying, pulverizing the resultingmixture into coarse particles (Japanese Patent Application ExaminedPublication No. 48-006622/1973). There is also proposed a method capableof producing spherical granules close to true spheres with few fibrousgranules at an almost constant grain size, comprising the steps of:granulation with a specified granulator and drying the resultinggranules (Japanese Patent Application Unexamined Publication No.6-166026/1994).

On the other hand, there is proposed a method comprising the steps of:dispersing a water-soluble nonionic cellulose ether powder whileallowing a cross-linking agent such as a dialdehyde to act on thesurface of the powder so as to prevent formation of lumps even in coldwater, and then destroying the crosslinked structure by the addition ofan alkali component to accelerate its solubility (Japanese PatentApplication Examined Publication No. 42-006674/1967). Further, there isproposed a method of producing a water-soluble nonionic cellulose etherwhich is free of dusting, has excellent water wettability and is solublein cold water in a short period of time without forming lumps,comprising the steps of: adding a crosslinking agent, an acid, and ahumectant to a water-soluble nonionic cellulose ether to obtain aparticulate material of which 30% by weight or less passes through a30-mesh sieve and of which 30% by weight or less remains on a 200-meshsieve (Japanese Patent Application Unexamined Publication No.2000-063565).

SUMMARY OF THE INVENTION

In the method of Japanese Patent Application Examined Publication No.48-006622/1973, the particles are once densified in the steps of mixingand drying, but become coarse particles having a fibrous portion, orfine powders or granules having a fiber on the surface thereof again inthe step of pulverizing, which will form lumps in cold water. In orderto improve such a defect, a large amount of water is added in the stepof mixing with the plasticizer to increase a loose apparent density, andthe resulting mixture is dried and pulverized. However, there isaccompanied with the drawback that the apparent density of the resultinggranules becomes too high so that it takes time to dissolve them. In themethod of Japanese Patent Application Unexamined Publication No.6-166026/1994, the produced spherical granules sometimes have thedrawback that it takes time to dissolve the granules in water becausethe water does not penetrate into the granules owing to poor wettabilityof the water-soluble cellulose ether.

In the methods of Japanese Patent Application Examined Publication No.42-006674/1967 and Japanese Patent Application Unexamined PublicationNo. 2000-063565, a dialdehyde or the like having mutagenicity is used sothat the methods may have problems of environmental hygiene. Further,addition of a crosslinking agent, for example, an expensive siliconcompound such as an alkylalkoxysilane including tetramethoxysilane,methyltrimethoxysilane and dimethyldimethoxysilane, sometimesdeteriorates compatibility so that the methods are not suited for theproduction of water-soluble nonionic cellulose ethers to be used forcosmetics or suspension polymerization agents.

In consideration of the above-described situations, the presentinvention has been made. An object of the invention is to provide aporous water-soluble nonionic cellulose ether having an improveddissolution rate in a small amount of water; and a production methodthereof.

The present inventors have carried out an extensive investigation with aview to achieving the above-described object. As a result, the presentinventors have found that a porous water-soluble nonionic celluloseether having an average pore size of 36 μm or smaller and an averageparticle size of from 30 to 300 μm is excellent in dissolution rate in asmall amount of water, leading to completion of the invention.

In one aspect of the invention, there is provided a porous water-solublenonionic cellulose ether having an average pore size of 36 μm or smallerand an average particle size of from 30 to 300 μm. In another aspect ofthe invention, there is provided a method for continuously producing aporous water-soluble nonionic cellulose ether having an average poresize of 36 μm or smaller and an average particle size of from 30 to 300μm, comprising the steps of: pulverizing a first water-soluble nonioniccellulose ether to obtain a first pulverized product, and sieving thefirst pulverized product through a sieve having an opening of from 40 to400 μm to obtain a first residue-on-sieve and a first sieve-passingfraction, wherein a portion or all of the first residue-on-sievecontaining particles having particle sizes smaller than and greater thanthe opening of the sieve is re-pulverized together with a secondwater-soluble nonionic cellulose ether in the step of pulverizing toobtain a second pulverized product, which is sieved to obtain the porouswater-soluble nonionic cellulose ether as a second sieve-passingfraction containing the re-pulverized particles; and wherein each of thefirst and second residues-on-sieve contains 10% by weight or more ofparticles having particle sizes smaller than the opening of the sieve.In a further aspect of the invention, there is provided a method forcontinuously producing a porous water-soluble nonionic cellulose etherhaving an average pore size of 36 μm or smaller and an average particlesize of from 30 to 300 μm, comprising the steps of: pulverizing a firstwater-soluble nonionic cellulose ether to obtain a first pulverizedproduct, and sieving the first pulverized product through a sieve havingan opening of from 40 to 400 μm to obtain a first residue-on-sieve and afirst sieve-passing fraction, wherein a portion or all of the firstresidue-on-sieve containing particles having particle sizes smaller thanand greater than the opening of the sieve, and a portion of the firstsieve-passing fraction, are re-pulverized together with a secondwater-soluble nonionic cellulose ether in the step of pulverizing toobtain a second pulverized product, which is sieved to obtain the porouswater-soluble nonionic cellulose ether as a second sieve-passingfraction containing the re-pulverized particles.

According to the invention, there can be provided a porous water-solublenonionic cellulose ether having an improved dissolution rate in a smallamount of water.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 shows an example of the sieving step according to the invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Examples of the porous water-soluble nonionic cellulose ether includealkyl celluloses, hydroxyalkyl celluloses and hydroxyalkyl alkylcelluloses. Examples of the alkyl celluloses include methyl cellulosehaving a DS value of from 1.0 to 2.2 and ethyl cellulose having a DSvalue of from 2.0 to 2.6. Examples of the hydroxyalkyl cellulosesinclude hydroxyethyl cellulose having an MS value of from 0.05 to 3.0and hydroxypropyl cellulose having an MS value of from 0.05 to 3.3.Examples of the hydroxyalkyl alkyl celluloses include hydroxyethylmethyl cellulose having a DS value of from 1.0 to 2.2 and an MS value offrom 0.1 to 0.6, hydroxypropyl methyl cellulose having a DS value offrom 1.0 to 2.2 and an MS value of from 0.1 to 0.6, and hydroxyethylethyl cellulose having a DS value of from 1.0 to 2.2 and an MS value offrom 0.1 to 0.6. The DS represents a degree of substitution and is thenumber of alkoxy groups present per glucose ring unit of cellulose; andthe MS represents a molar substitution and is an average molar number ofhydroxyalkoxy groups added per glucose ring unit of cellulose. These DSand MS can be calculated from values measured based on JapanesePharmacopoeia 16th Edition.

The porous water-soluble nonionic cellulose ether has an average poresize of 36 μm or smaller, more preferably 33 μm or smaller, morepreferably 30 μm or smaller, from the standpoint of uniform distributionof water and promotion of dissolution of the water-soluble nonioniccellulose ether. When the porous water-soluble nonionic cellulose etherhas an average pore size greater than 36 μm, it cannot have an excellentdissolution rate in a small amount of water. The lower limit of theaverage pore size is preferably 20 μm for keeping the polymerizationdegree. The term “average pore size” means a median diameter incumulative pore volume distribution when pores are measured whileregarding each shape of the pores as a cylinder and it includes pores onthe surfaces of the particles and voids between the particles. Theaverage pore size can be measured by using, as a measuring and analyzingapparatus, a mercury intrusion porosimeter (for example, “AutoPore9520”, product of Shimadzu Corporation) and subjecting about 0.05 g of asample in a standard cell to measurement under the initial mercurypressure of 7 kPa.

A water-soluble nonionic cellulose ether having an average pore size of36 μm or smaller has not conventionally been available because it isirrational to return a portion of a pulverized product containingparticles having particle sizes smaller than the opening of a sieve usedin a sieving step to the pulverization step for re-pulverization in viewof preferential achievement of efficient pulverization, improvedproductivity and sharp particle size distribution. According to theinvention, for the first time, it becomes possible to provide awater-soluble nonionic cellulose ether having an average pore size of 36μm or smaller by returning a portion or all of a pulverized productcontaining particles having particle sizes smaller than the opening of asieve used in a sieving step to a pulverization step forre-pulverization.

The porous water-soluble nonionic cellulose ether has an averageparticle size of from 30 to 300 μm, preferably from 30 to 150 μm, morepreferably from 30 to 100 μm, still more preferably from 30 to 70 μm,particularly preferably from 30 to 65 μm. When the porous water-solublenonionic cellulose ether has an average particle size smaller than 30μm, an excellent dissolution rate in a small amount of water may not beobtained, and aggregation among porous water-soluble nonionic celluloseether particles hinders the dissolution. When the porous water-solublenonionic cellulose ether has an average particle size greater than 300μm, an excellent dissolution rate in a small amount of water cannot beobtained. The average particle size can be measured by using a laserdiffraction particle size analyzer (for example, “HELOS&RODOS”, productof Sympatec GmbH) and selecting a measurement concentration of 2% byweight, measurement time of 2 seconds and a shape factor of 1.0.

The porous water-soluble nonionic cellulose ether contains, based on thetotal weight, preferably 5% by weight or more, more preferably 6% byweight or more, still more preferably 7% by weight or more of particleshaving particle sizes smaller than 15 μm; preferably 2% by weight ormore, more preferably 3% by weight or more of particles having particlesizes smaller than 10 μm; and preferably 1% by weight or more, morepreferably 2% by weight or more of particles having particle sizessmaller than 5 μm from the standpoint of achieving an excellentdissolution rate in a small amount of water. The particle sizedistribution can be allowed to fall within the above-described ranges bycontrolling a returning amount of the pulverized product, which containsparticles having particle sizes smaller than the opening of the sieveused in the sieving step, to the pulverization step forre-pulverization.

A loose apparent density of the porous water-soluble nonionic celluloseether is preferably from 0.20 to 0.50 g/ml, more preferably from 0.22 to0.38 g/ml from the standpoint of achieving an excellent dissolution ratein a small amount of water. The term “loose apparent density” means abulk density in a loosely packed state and it can be measured by amethod comprising the steps of: uniformly feeding a sample into acylindrical stainless container having a diameter of 5.03 cm and aheight of 5.03 cm (volume: 100 ml) from 23 cm above the containerthrough a JIS 22-mesh sieve having opening of 710 μm; leveling the uppersurface of the cylindrical container; and weighing the container havingthe upper surface leveled.

The viscosity at 20° C. of a 2% by weight aqueous solution of the porouswater-soluble nonionic cellulose ether is preferably from 100 to 600,000mPa·s, more preferably from 3,000 to 300,000 mPa·s, still morepreferably from 5,000 to 200,000 mPa·s from the standpoint of shaperetention or solubility. The viscosity at 20° C. of a 2% by weightaqueous solution of the porous water-soluble nonionic cellulose ethercan be measured using Brookfield type viscometer LV, which is a singlecylinder-type rotational viscometer, in accordance with ViscosityMeasurement Method II of hypromellose in Japanese Pharmacopoeia 16thEdition.

The dissolution time of the porous water-soluble nonionic celluloseether can be made shorter by preferably 10% or more, more preferably 20%or more than that of a conventional product. More specifically, it ispreferably 160 seconds or less, more preferably 140 seconds or less,still more preferably 120 seconds or less. The dissolution time means atime at which a torque value becomes constant after 1 kg of awater-soluble nonionic cellulose ether is introduced in a 5-L sigmadouble-arm kneader equipped with a torque meter and then 1.5 kg of waterof 20° C. is introduced therein at once while mixing them at 60 rpm.

The porous water-soluble nonionic cellulose ether shows an excellentdissolution property even in a small amount of water. For example, whenthe water-soluble nonionic cellulose ether is dissolved in water byusing a proper kneading apparatus such as a kneader or a roll mill, aweight ratio of the water to the water-soluble nonionic cellulose etheris preferably from 0.6 to 99, more preferably from 1 to 20.

Since the porous water-soluble nonionic cellulose ether has an excellentdissolution property even in a small amount of water, it is usable as adrug or food binder, a disintegrant, a thickening agent for varioustypes of solvents, a water retention agent for building materials, or abinder for extrusion molding.

Next, the method for continuously producing a porous water-solublenonionic cellulose ether will be described.

A water-soluble nonionic cellulose ether can be produced using theconventional method, for example, the following method.

First, in an etherification step for reacting an alkali cellulose withan etherifying agent, a reaction product (i.e. crude cellulose ether)can be obtained. The alkali cellulose can be obtained by bringing asolution of an alkali metal hydroxide such as sodium hydroxide intocontact with a pulp such as wood pulp or linter pulp.

Preparation of an alkali cellulose and reaction thereof with anetherifying agent may be carried out simultaneously in the presence ofboth the solution of an alkali metal hydroxide and the etherifyingagent. Alternatively, the alkali cellulose may be prepared and thenreacted with the etherifying agent. Examples of the etherifying agentinclude alkyl halides such as methyl chloride, ethylene oxide andpropylene oxide.

The reaction product (i.e. crude cellulose ether) obtained in theetherification step is then subjected to a washing step typicallycomprising a washing stage and a filtering stage and/or pressing stage,so that a water-soluble nonionic cellulose ether is obtained.

The resulting water-soluble nonionic cellulose ether is then typicallysubjected to drying and pulverization steps to provide a water-solublenonionic cellulose ether as a final product. Drying may be carried outsimultaneously with pulverization, or drying may be followed bypulverization.

A known pulverizer can be used. Examples of the pulverizer include animpact mill, an oscillating mill, a ball mill, a roller mil, and a turbomill.

After the pulverization step, a pulverized product taken out from thepulverizer is allowed to pass through a sieve to obtain aresidue-on-sieve and a sieve passing fraction. The sieve-passingfraction is collected as a product. Thus, a water-soluble nonioniccellulose ether powder is obtained. The sieve has an opening ofpreferably from 40 to 400 μm, more preferably from 100 to 350 μm.

When the sieve has an opening of 40 μm or greater but smaller than 100μm, the porous water-soluble nonionic cellulose ether has an averageparticle size of preferably from 30 to 39 μm. When the sieve has anopening of 100 μm or greater but smaller than 300 μm, the porouswater-soluble nonionic cellulose ether has an average particle size ofpreferably from 40 to 100 μm. When the sieve has an opening of from 300to 400 μm, the porous water-soluble nonionic cellulose ether has anaverage particle size of preferably from 100 to 300 μm.

A feed rate of the pulverized product per sieve area is variabledepending on a sieve area, intensity of oscillation or tapping of thesieve, pulverization ability of the pulverizer, a feed rate of a new rawmaterial to the pulverizer and the like. The feed rate of the pulverizedproduct per sieve area is preferably from 0.2 to 20 ton/m²/hour, morepreferably from 0.5 to 10 ton/m²/hour when the pulverizer is understeady operation. When the feed rate is below 0.2 ton/m²/hour, a porouswater-soluble nonionic cellulose ether may not be obtained even when aportion of the pulverized product is returned to the pulverizer. Whenthe feed rate is more than 20 ton/m²/hour, excessively large equipmentmay be required. More specifically, when the sieve has an opening of 40μm or greater but smaller than 100 μm, a feed rate of the pulverizedproduct per sieve area is preferably from 0.2 to 0.5 ton/m²/hour; whenthe sieve has an opening of 100 μm or greater but smaller than 300 μm, afeed rate of the pulverized product per sieve area is preferably from0.2 to 1.0 ton/m²/hour; and when the sieve has an opening of from 300 to400 μm, a feed rate of the pulverized product per sieve area ispreferably from 0.5 to 1.0 ton/m²/hour.

After sieving, a portion or all of the residue-on-sieve is mixed with awater-soluble cellulose ether which will be pulverized in thepulverization step to obtain a pulverization mixture.

A portion or all of the residue-on-sieve is required to contain bothparticles having particle sizes smaller than the opening of the sieveand particles having particle sizes greater than the opening of thesieve. The lower limit of the content of the particles having particlesizes smaller than the opening of the sieve in the residue-on-sieve ispreferably 10% by weight or more, more preferably 20% by weight or more,still more preferably 50% by weight or more. The upper limit of thecontent of the particles having particle sizes smaller than the openingof the sieve in the residue-on-sieve is preferably 90% or less, morepreferably 80% or less, still more preferably 70% or less. When thecontent is more than 90%, the through-put of the pulverization maydrastically decrease and the productivity may be deteriorated.

As the particles having particle sizes smaller than the opening of thesieve, a portion of the sieve-passing fraction may be mixed with aportion or all of the residue-on-sieve. A proportion of theresidue-on-sieve in the pulverized product to be returned to thepulverizer for re-pulverization can be controlled by adjusting the feedrate of the pulverized product per sieve area. As the feed rate of thepulverized product per sieve area increases, there is an increase in aproportion of particles which have particle sizes smaller than theopening of the sieve in the pulverized product, and which have notpassed through the sieve, and which will be returned to the pulverizer.The proportion of particles having particle sizes smaller than theopening of the sieve in the pulverized product to be returned to thepulverizer can be adjusted by changing the total sieve area of aplurality of sieves with increase or decrease in the number of sieves tobe used; or by reducing the contact area of powder to the sieve with aportion of the sieve sealed or with a dam installed.

The proportion of particles having particle sizes smaller than theopening of the sieve in the pulverized product to be returned to thepulverizer can be measured using a method comprising the steps ofsufficiently tapping a sieve having an opening equal to that of theabove-described sieve and having the pulverized product thereon; andmeasuring the weight of particles which have passed through the sieve.The sieve to be used for the measurement has an inner diameter of from75 to 300 mm, the amount of the powder is from 20 to 100 g, and tappingtime is one minute or more, preferably from 5 to 40 minutes.

An amount of the pulverized product, which contains a portion or all ofthe residue-on-sieve and an optional portion of sieve-passing fractionand will be re-pulverized together with the un-pulverized water-solublenonionic cellulose ether, is preferably from 0.2 to 6 times, morepreferably from 1.0 to 4.5 times, on dry weight basis, of the wholeamount of the un-pulverized water-soluble nonionic cellulose ether to bepulverized together by the pulverizer in the pulverization step.

An example of the method for continuously producing a porouswater-soluble nonionic cellulose ether having an excellent dissolutionproperty even in a small amount of water will next be describedreferring to FIG. 1 .

A water-soluble nonionic cellulose ether 1 is pulverized using apulverizer 11. The pulverizer may be an apparatus which simultaneouslypulverizes and dries a hydrous water-soluble nonionic cellulose etherafter washing, or may be an apparatus which pulverizes a water-solublenonionic cellulose ether dried after washing. The pulverized product 2thus obtained is sieved with a sieve 12 having an opening of from 40 to400 μm to obtain a residue-on-sieve containing 10% by weight or more ofparticles having particle sizes smaller than the opening, as well as asieve-passing fraction. Then, a portion or all 3 of the residue-on-sieveis mixed with a water-soluble nonionic cellulose ether to be pulverizedin the pulverizer 11 and then re-pulverized. The sieve-passing fractionis introduced into a product tank as a water-soluble nonionic celluloseether 5 as a non-porous product.

The sieve-passing fraction is divided into two portions by installationof a damper in a pipe or a conveyor in which or on which thesieve-passing fraction moves. One portion, water-soluble nonioniccellulose ether 5, is introduced into a product tank as a product, whilethe other portion, a sieve-passing portion 4, is optionally returned tothe pulverizer 11 for re-pulverization together with theresidue-on-sieve 3. In this case, the amount to be returned to thepulverizer can be controlled by adjusting the angle of the damper or thelike. The amount to be returned to the pulverizer can also be controlledby alternately switching the damper to a product tank side or a returnside by setting a timer to change a division ratio. The division ratiocan be adjusted so that the weight content of particles having particlesizes smaller than the opening of the sieve in the pulverized product tobe returned to the pulverizer falls within a preferable range.

EXAMPLES

The invention will hereinafter be explained specifically by Examples andComparative Examples. It should not be construed that the invention islimited to or by Examples.

The physical properties of porous or non-porous water-soluble celluloseethers obtained in Examples and Comparative Examples were measured usingthe following method.

<Method of Measuring the Content of Particles Having Particle SizesSmaller than an Opening of a Sieve in a Pulverized Product>

A pulverized product (50 g) was placed on a sieve having an innerdiameter of 200 mm and having an opening equal to that of a sieveprovided at an outlet of a pulverizer, and was subjected to tapping for20 minutes. A weight of particles having passed through the sieve wasmeasured.

<Average Pore Size>

The 0.05 g of a water-soluble cellulose was placed in a standard celland an average pore size was measured at an initial mercury pressure of7 kPa using a mercury intrusion porosimeter (“Autopore 9520”, product ofShimadzu Corporation).

<Average Particle Size>

An average particle size was measured by using a laser diffractionparticle size distribution analyzer (“HELOS&RODOS”, product of SympatecGmbH) and selecting a measurement concentration of 2% by weight,measurement time of 2 seconds, and a shape factor of 1.0.

<Particle Size Distribution>

A sieving method was used.

<Loose Apparent Density>

A loose apparent density was measured in a method comprising the stepsof: feeding a sample uniformly into a cylindrical stainless vesselhaving a diameter of 5.03 cm and a height of 5.03 cm (volume: 100 ml)from 23 cm above the vessel through a JIS 22-mesh sieve having openingof 710 μm; leveling the upper surface; and weighing the vessel havingthe upper surface leveled.

<Viscosity at 20° C. of a 2% by Weight Aqueous Solution>

The viscosity was measured using Brookfield type viscometer LV, whichwas a single cylinder-type rotational viscometer, in accordance withViscosity Measurement Method II of hypromellose in JapanesePharmacopoeia 16th Edition.

<Measurement of Dissolution Time>

Dissolution time was measured in a method comprising the steps ofintroducing 1 kg of a water-soluble cellulose ether in a 5-L sigmadouble-arm kneader equipped with a torque meter; adding 1.5 kg of waterof 20° C. into the kneader at once while mixing at 60 rpm; monitoring atime-dependent change of torque by a torque meter; and measuring time atwhich a torque became constant after gradual increase. The time requiredto make a torque constant was regarded as the dissolution time of thewater-soluble cellulose ether.

Example 1

In a pressure vessel equipped with an internal stirrer, 1.98 parts byweight of 49% by weight sodium hydroxide, 1.60 parts by weight of methylchloride for methoxy substitution, and 0.21 part by weight of propyleneoxide for hydroxypropoxy substitution were added to 1.00 part by weightof a wood pulp. The resulting mixture was allowed to react at atemperature of from 60 to 90° C. for 2 hours to obtain a crude product.Hot water of 95° C. in an amount of 20 times of the weight of thehydroxypropyl methyl cellulose was then added therein to disperse thecrude product and the resulting dispersion was filtered to obtain awashed cake. Hot water of 95° C. in an amount of 10 times of the weightof hydroxypropyl methyl cellulose was added to the washed cake and theresulting mixture was filtered to obtain a washed cake having a watercontent of 50% by weight. After the water content of the washed cake wasincreased to 65% by weight in addition of water, the washing cake wasdried to obtain fibrous hydroxypropyl methyl cellulose having residualsalt content of 1% by weight and water content of 1.2% by weight. Thefibrous hydroxypropyl methyl cellulose thus obtained had a DS value of1.8 and an MS value of 0.15 (Table 1).

The fibrous hydroxypropyl methyl cellulose was continuously fed to aball mill at a rate of 150 kg/hour. The ball mill had, at the outlethereof, a sieve having an opening of 250 μm and a sieve area of 1 m²,through which the milled product discharged from the ball mill wassieved at a feed rate of the milled product to the sieve of 0.5ton/m²/hour.

All of the residue-on-sieve, which was the milled product containing 40%by weight of particles having particle sizes smaller than the opening ofthe sieve and 60% by weight of particles having particle sizes equal toor greater than the opening of the sieve, was returned to the inlet ofthe ball mill at a rate of 350 kg/hour and was re-milled together withun-milled hydroxypropyl methyl cellulose. The weight of the milledproduct to be returned to the milling step was 2.3 times (350/150) ofthe weight of the un-milled hydroxypropyl methyl cellulose.

The product having passed through the sieve was collected in a producttank at a rate of 150 kg/hour as porous hydroxypropyl methyl cellulose.The physical properties of the porous hydroxypropyl methyl cellulosethus obtained were measured using the above-described methods. As aresult, the average pore size was 30 μm; the average particle size was60 μm; with respect to the particle size distribution, the content ofparticles smaller than 15 μm was 6% by weight, the content of particlessmaller than 10 μm was 2% by weight, and the content of particlessmaller than 5 μm was 1% by weight; and the loose apparent density was0.25 g/ml. The viscosity at 20° C. of a 2% by weight aqueous solutionwas 4,000 mPa·s and the dissolution time was 120 seconds (Table 2).

Example 2

In the same manner as in Example 1 except that the wood pulp wasreplaced by a cotton linter pulp and 1.30 parts by weight of 49% byweight sodium hydroxide, 1.13 parts by weight of methyl chloride and0.27 part by weight of propylene oxide were used with respect to 1.00part by weight of the cotton linter pulp, the reaction, washingcontaining a washing stage and a filtering stage, and drying werecarried out to obtain fibrous hydroxypropyl methyl cellulose having a DSvalue of 1.5 and an MS value of 0.20 (Table 1).

The fibrous hydroxypropyl methyl cellulose was continuously fed to aroller mill at a rate of 150 kg/hour. The roller mill had, at the outlethereof, the same sieve as in Example 1, through which the milled productdischarged from the roller mill was sieved at a feed rate of the milledproduct to the sieve of 0.3 ton/m²/hour. The product having passedthrough the sieve was collected in a product tank at a rate of 150kg/hour.

A portion of the residue-on-sieve, which was the milled productcontaining 30% by weight of particles having particle sizes smaller thanthe opening of the sieve and 70% by weight of particles having particlesizes equal to or greater than the opening of the sieve, was returned tothe inlet of the roller mill at a rate of 150 kg/hour and was re-milledtogether with un-milled hydroxypropyl methyl cellulose. The weight ofthe milled product to be returned to the milling step was 1.0 time(150/150) of the weight of the un-milled hydroxypropyl methyl cellulose.

The physical properties of the porous hydroxypropyl methyl cellulosethus obtained were measured in the same manner as in Example 1. Theresults are shown in Table 2.

Example 3

In the same manner as in Example 1 except that 2.83 parts by weight of49% by weight sodium hydroxide, 2.13 parts by weight of methyl chlorideand 0.53 part by weight of propylene oxide were used with respect to1.00 part by weight of the same pulp as in Example 1, the reaction andwashing containing a washing stage and a filtering stage were carriedout. After the washing, water was added to a washed cake to increase thewater content thereof to 65% by weight to obtain hydrous hydroxypropylmethyl cellulose having a DS value of 1.90 and an MS value of 0.25(Table 1).

The hydrous hydroxypropyl methyl cellulose was fed to an impact mill ata rate of 150 kg/hour on dry weight basis. Hot air was sent to theimpact mill at the same time, so that milling and drying were carriedout simultaneously. The impact mill had, at the outlet hereof, the samesieve as in Example 1, through which the milled product discharged fromthe impact mill was sieved at a feed rate of the milled product to thesieve of 0.2 ton/m²/hour. The product having passed through the sievewas collected in a product tank at a rate of 150 kg/hour.

A portion of the residue-on-sieve, which was the milled productcontaining 20% by weight of particles having particle sizes smaller thanthe opening of the sieve and 80% by weight of particles having particlesizes equal to or greater than the opening of the sieve, was returned tothe inlet of the impact mill at a rate of 50 kg/hour and was re-milledtogether with un-milled hydroxypropyl methyl cellulose. The weight ofthe milled product to be returned to the milling step was 0.3 time(50/150) of the weight of the un-milled hydroxypropyl methyl cellulose.

The physical properties of the porous hydroxypropyl methyl cellulosethus obtained were measured in the same manner as in Example 1. Theresults are shown in Table 2.

Example 4

In the same manner as in Example 1 except that 2.83 parts by weight of49% by weight sodium hydroxide and 2.13 parts by weight of methylchloride for methoxy substitution were added to 1.00 part by weight ofthe same pulp as in Example 1, the reaction, washing containing awashing stage and a filtering stage, and subsequent drying were carriedout to obtain fibrous methyl cellulose having a DS value of 1.8 (Table1).

The fibrous methyl cellulose was continuously fed to a turbo mill at arate of 150 kg/hour. The turbo mill had, at the outlet hereof, the samesieve as in Example 1, through which the milled product discharged fromthe turbo mill was sieved at a feed rate of the milled product to thesieve of 0.6 ton/m²/hour. The 80% by weight of the product having passedthrough the sieve was collected in a product tank at a rate of 150kg/hour.

The remaining 20% by weight portion of the product having passed throughthe sieve and the residue-on-sieve were returned to the inlet of theturbo mill at a rate of 37.5 kg/hour and 412.5 kg/hour, respectively.Eventually, a portion of the milled product containing 50% by weight ofsum of the particles of the residue-on-sieve having particle sizessmaller than the opening of the sieve and the particles having passedthrough the sieve and 50% by weight of the particles of theresidue-on-sieve having particle sizes equal to or greater than theopening of the sieve was re-milled together with an un-milledhydroxypropyl methyl cellulose. The weight of the milled product to bereturned to the milling step was 3.0 times (450/150) of the weight ofthe un-milled hydroxypropyl methyl cellulose.

The physical properties of the porous methyl cellulose thus obtainedwere measured in the same manner as in Example 1. The results are shownin Table 2.

Example 5

In the same manner as in Example 4 except for use of a wood pulp havinga polymerization degree higher than that of the wood pulp used inExample 4, the reaction, washing containing a washing stage and afiltering stage, and subsequent drying were carried out to obtainfibrous methyl cellulose having a DS value of 1.8 (Table 1).

The fibrous methyl cellulose was continuously fed to a roller mill at arate of 150 kg/hour. The roller mill had, at the outlet thereof, thesame sieve as in Example 1, through which the milled product dischargedfrom the roller mill was sieved at a feed rate of the milled product tothe sieve of 0.7 ton/m²/hour. The product having passed through thesieve was collected in a product tank at a rate of 150 kg/hour.

All of the residue-on-sieve, which was the milled product containing 50%by weight of particles having particle sizes smaller than the opening ofthe sieve and 50% by weight of particles having particle sizes equal toor greater than the opening of the sieve, was returned to the inlet ofthe roller mill at a rate of 550 kg/hour and was re-milled together withun-milled hydroxypropyl methyl cellulose. The amount of the milledproduct to be returned to the milling step was 3.7 times (550/150) ofthe amount of the un-milled methyl cellulose.

The physical properties of the methyl cellulose thus obtained weremeasured in the same manner as in Example 4. The results are shown inTable 2.

Example 6

In the same manner as in Example 1 except that the wood pulp wasreplaced by a cotton linter pulp and 1.30 parts by weight of 49% byweight sodium hydroxide, 1.13 parts by weight of methyl chloride and0.27 part by weight of propylene oxide were used with respect to 1.00part by weight of the cotton linter pulp, the reaction, washingcontaining a washing stage and a filtering stage, and subsequent dryingwere carried out to obtain fibrous hydroxypropyl methyl cellulose havinga DS value of 1.5 and an MS value of 0.20 (Table 1).

The fibrous hydroxypropyl methyl cellulose was continuously fed to aturbo mill at a rate of 150 kg/hour. The turbo mill had, at the outlethereof, the same sieve as in Example 1, through which the milled productdischarged from the turbo mill was sieved at a feed rate of the milledproduct to the sieve of 0.8 ton/m²/hour. The product having passedthrough the sieve was collected in a product tank at a rate of 150kg/hour.

All of the residue-on-sieve, which was the milled product containing 55%by weight of particles having particle sizes smaller than the opening ofthe sieve and 45% by weight of particles having particle sizes equal toor greater than the opening of the sieve was returned to the inlet ofthe turbo mill at a rate of 650 kg/hour and was re-milled together withun-milled hydroxypropyl methyl cellulose. The weight of the milledproduct to be returned to the milling step was 4.3 times (650/150) ofthe weight of the un-milled hydroxypropyl methyl cellulose.

The physical properties of the hydroxypropyl methyl cellulose thusobtained were measured in the same manner as in Example 1. The resultsare shown in Table 2.

Example 7

In the same manner as in Example 1 except that the wood pulp wasreplaced by a cotton linter pulp and 1.98 parts by weight of 49% byweight sodium hydroxide, 1.60 parts by weight of methyl chloride and0.21 part by weight of propylene oxide were used with respect to 1.00part by weight of the cotton linter pulp, the reaction and washingcontaining a washing stage and a filtering stage were carried out. Afterthe washing, water was added to a washed cake to increase the watercontent thereof to 65% by weight to obtain hydrous hydroxypropyl methylcellulose having a DS value of 1.8 and an MS value of 0.15 (Table 1).

The hydrous hydroxypropyl methyl cellulose was fed to an impact mill ata rate of 150 kg/hour on dry weight basis. Hot air was sent to theimpact mill at the same time so that milling and drying were carried outsimultaneously. The impact mill had, at the outlet hereof, a sievehaving an opening of 63 μm and a sieve area of 1.0 m², through which themilled product discharged from the impact mill was sieved at a feed rateof the milled product to the sieve of 0.4 ton/m²/hour. The producthaving passed through the sieve was collected in a product tank at arate of 150 kg/hour.

All of the residue-on-sieve, which was the milled product containing 55%by weight of particles having particle sizes smaller than the opening ofthe sieve and 45% by weight of particles having particle sizes equal toor greater than the opening of the sieve, was returned to the inlet ofthe impact mill at a rate of 250 kg/hour and re-milled together withun-milled hydroxypropyl methyl cellulose. The weight of the milledproduct to be returned to the milling step was 1.7 times (250/150) ofthe weight of the un-milled hydroxypropyl methyl cellulose.

The physical properties of the hydroxypropyl methyl cellulose thusobtained were measured in the same manner as in Example 1. The resultsare shown in Table 2.

Example 8

In the same manner as in Example 7, hydrous hydroxypropyl methylcellulose having a DS value of 1.8 and an MS value of 0.15 and havingwater content of 65% by weight was obtained (Table 1).

The hydrous hydroxypropyl methyl cellulose was fed to an impact mill ata rate of 50 kg/hour on dry weight basis. Hot air was sent to the impactmill at the same time so that milling and drying were carried outsimultaneously. The impact mill had, at the outlet hereof, a sievehaving an opening of 63 μm and a sieve area of 1.0 m², through which themilled product discharged from the impact mill was sieved at a feed rateof 0.095 ton/m²/hour. The 90% by weight of the product having passedthrough the sieve was collected in a product tank at a rate of 45kg/hour.

The remaining 10% by weight of the product having passed through thesieve and the residue-on-sieve were returned to the inlet of the impactmill at a rate of 5 kg/hour and 45 kg/hour, respectively. Eventually, aportion of the milled product containing 20% by weight in sum of theparticles of the residue-on-sieve having particle sizes smaller than theopening of the sieve and the particles having passed through the sieveand 80% by weight of the particles of the residue-on-sieve havingparticle sizes equal to or greater than the opening of the sieve wasreturned to the inlet of the impact mill at a rate of 50 kg/hour and wasre-milled together with un-milled hydroxypropyl methyl cellulose. Theweight of the milled product to be returned to the milling step was 1.0time (50/50) of the weight of the un-milled hydroxypropyl methylcellulose.

The physical properties of the hydroxypropyl methyl cellulose thusobtained were measured in the same manner as in Example 1. The resultsare shown in Table 2.

Comparative Example 1

In the same manner as in Example 7, hydrous hydroxypropyl methylcellulose having a DS value of 1.8 and an MS value of 0.15 and havingwater content of 65% by weight was obtained (Table 1).

The hydrous hydroxypropyl methyl cellulose was fed to an impact mill ata rate of 80 kg/hour on dry mass basis. Hot air was sent to the impactmill at the same time so that milling and drying were carried outsimultaneously. The impact mill had, at the outlet thereof, the samesieve as in Example 8 and the milled product was sieved under the sameconditions as in Example 8. The product having passed through the sievewas collected in a product tank at a rate of 80 kg/hour.

The milled product not having passed through the sieve was returned tothe inlet of the impact mill at a rate of 10 kg/hour, without beingmixed with the milled product having passed through the sieve, and wasre-milled. The weight of the milled product to be returned to themilling step was 0.13 time (10/80) of the weight of an un-milledhydroxypropyl methyl cellulose.

The physical properties of the resulting hydroxypropyl methyl cellulosewere measured in the same manner as in Example 1. The results are shownin Table 2.

TABLE 1 water-soluble nonionic cellulose pulverization conditions etherfeed rate of substitution groups pulverized re-pulverization hydroxy-product to sieve pulverized product to *1 methoxy propoxy pulverizer{t/(m²/hour)} be re-pulverized (wt %) (DS) (MS) Example 1 ball mill 0.5residue-on-sieve 40 1.8 0.15 Example 2 roll mill 0.3 residue-on-sieve 301.5 0.20 Example 3 impact dryer mill 0.2 residue-on-sieve 20 1.9 0.25Example 4 turbo mill 0.6 residue-on-sieve and 50 1.8 — sieve-passingfraction Example 5 roll mill 0.7 residue-on-sieve 50 1.8 — Example 6turbo mill 0.8 residue-on-sieve 55 1.5 0.20 Example 7 impact dryer mill0.4 residue-on-sieve 55 1.8 0.15 Example 8 impact dryer mill 0.1residue-on-sieve and 20 1.8 0.15 sieve-passing fraction Comp. Ex. 1impact dryer mill 0.1 residue-on-sieve 0 1.8 0.15 *1 The content of theparticles having smaller particle sizes than opening of the sieve in thepulverized product which will be re-pulverized.

TABLE 2 physical properties of porous water-soluble nonionic celluloseether average average loose viscosity pore particle particle sizeapparent of 2 wt % dissolution diameter size <15 μm <10 μm <5 μm densityaq. solution time (μm) (μm) (wt %) (wt %) (wt %) (g/ml) (mPa · s)(seconds) Example 1 30 60 6 2 1 0.25 4000 120 Example 2 32 70 5 2 1 0.24100000 130 Example 3 35 62 6 2 1 0.33 8000 150 Example 4 28 55 6 2 20.26 8000 119 Example 5 27 50 7 3 2 0.26 30000 115 Example 6 30 40 8 3 20.35 100000 122 Example 7 30 35 9 4 3 0.35 100000 140 Example 8 36 37 94 3 0.35 100000 153 Comp. Ex. 1 38 40 8 3 2 0.35 100000 170

The invention claimed is:
 1. A porous water-soluble nonionic celluloseether having an average pore size of 36 μm or smaller and an averageparticle size of from 30 to 300 μm.
 2. The porous water-soluble nonioniccellulose ether according to claim 1, comprising 5% by weight or more ofparticles having particle sizes smaller than 15 μm, 2% by weight or moreof particles having particle sizes smaller than 10 μm, and 1% by weightor more of particles having particle sizes smaller than 5 μm.
 3. Theporous water-soluble nonionic cellulose ether according to claim 1,having a loose apparent density of from 0.20 to 0.50 g/ml.